Process for reducing the patulin concentration in fruit juices

ABSTRACT

A procedure for reducing the patulin content in a fruit juice which includes presenting the juice to a resin material having in abundance micropores of less than 20 Å minimum pore width and at least a pore surface capable of retaining patulin by the forces of chemisorption. Preferably the resin has weak base functionality and is substantially devoid of mesopores and macropores. The resin preferably has a surface area of greater than 900 m 2 /g (BET) and the resin has been hypercross-linked whilst in the swollen state. Regeneration involves the conversion of the resin held patulin to a more easily flushed out derivative using ammonia or a volatile base, preferably generated in situ from a high pH solution.

The invention concerns a process for reducing the patulin concentrationin fruit juices, apparatus suitable for such a purpose and to relatedmethods and means.

Patulin 4-Hydroxy-4H-furo[3,2-c]pyran-2(6H)-one (See Formula 1) is amycotoxin produced by certain species of the genera Aspegillus andPenicillium. It is common in fruit that is rotting prior to processingfor juice production. Penicillium expansum, is one such fungus and it isresponsible for decomposition of apples and other fruit.

Apples destined for processing into juice production frequently are packhouse rejects, wind falls, weather damaged or from cold storage. Thefruit is often stored in the open for extended periods beforeprocessing. The percentage of fruit with varying degrees of rot can behigh and inevitably will contain patulin.

The United Kingdom Ministry of Agriculture, Fisheries and Food in itsFood Surveillance Paper No. 36 (1993) “Mycotoxins “Third Report”indicates that Penicillium expansum which produces patulin is a commonstorage rot in a diverse range of product(e.g. apples, peaches, pears,bananas, pineapples, apricots, cherries and grapes). They indicate thatfor apple juices patulin levels are generally higher in cloudy juicesthan in clear juices (highest levels in their data showed as 434 μg/kgand 118 μg/kg respectively).

Mycotoxins are undesirable in food because of their toxicity to animalsand potential toxicity to human beings. The toxic activity of patulin,its teratogenicity, carcinogenicity and mutagenicity is known and is ofconcern.

The Codex Alimentarius Commission as part of the United Nations jointFAO/WHO Food Standards Programme in their 28th Session (June 1997) inrespect of patulin indicates a PMTDI (Provisional Maximum TolerableIntake) of 0.4 micrograms per kilogram body weight per day (i.e. 0.4μg/kg.bw/day).

Apple juice can occasionally be heavily contaminated) notwithstandingthat apple juice generally (particularly single strength apple juice eg;11.5° Brix) has patulin levels of below 50 μg/l (micrograms per liter).

We believe that lower recommendations (eg; to below 25 μg/kg of patulin)are now being considered.

We have found in some apple juice samples (where there is a significantuse of windfall and/or rotting fruit) to be as high as 1500 μg/l.However apple juice more commonly contains patulin up to 200 μg/l.Nevertheless a significant task exists in meeting targets for patulincontent.

Different active and passive processes for reducing the patulin level tobelow the arbitrary limits mentioned are known. It is known that addingascorbic acid or sulfur dioxide destroys patulin. However the additionof sulfur dioxide is legally not allowed in commercial operations.

Patulin also degrades in time in stored juice. The gradual loss ofpatulin from juice on storage is not a practical solution to providingjuice with acceptable patulin levels.

Alcoholic fermentation of fruit juice is also reported to destroypatulin.

Some grades of activated carbon are effective at adsorbing patulin fromjuice. Dosages in the range 1˜2 g/l provide up to 80% patulin reduction.Activated carbon can be used commercially to reduce patulin from fruitjuice, but it is difficult to handle and is an expensive consumableitem. Activated carbon is not viable to regenerate and reuse. It alsoadds to the solids loading of the factory effluent creatingenvironmental problems.

It is an object of the present invention to provide a commerciallyviable process and/or apparatus for reducing the patulin concentrationin fruit juices. It also involves providing (e.g. regenerationprocedures and the products of any such processes or procedures) relatedprocedures, methods and means.

In a first aspect the present invention consists in a process forreducing the patulin content in a fruit juice which comprises orincludes

(i) presenting the juice to a resin material having in abundancemicropores of less than 20 Å minimum pore width (“mpw”) and at least apore surface capable of retaining patulin by the forces of chemisorption(for example, van der Waal and London dispersion interactions), and

(ii) harvesting the juice with a reduced patulin content from step (i).

The adsorption of patulin onto the surface of the micropores of theresin is dependent upon the plurality of the surface matrix andorientation of the polar groups on the patulin molecule. The forces ofchemisorption are likely provided by van der Waal and London dispersioninteractions. The energy of chemisorption is very small and the patulinmolecules are able to undergo lateral diffusion and conformationalchanges on surrounding surfaces. Therefore the chemisorption is bestdescribed as the physical attraction on to a chemically inert adsorptionsurface.

Preferably the resin has weak base functionality althoughnon-functionaries yet wettable resins may be used.

Preferably said resin is substantially devoid of mesopores andmacropores.

It is believed that the resin and its micropores is such that causticsoda is substantially ineffective in chemically converting the microporeheld patulin to a more easily flushed out patulin derivative.

Preferably said process uses a resin having very high internal surfaceareas yet a low mercury intrusion characteristic.

Preferably said resin has a surface area of greater than 900 (eg; from900 to 1500) m²/g (BET).

Preferably said surface area is from 1000 to 1500 m²/g (BET).

Preferably said resin has a mercury intrusion (d₅₀,A) of less than 100.

Preferably said resin has micropores in abundance of less than 15 Å(mpw).

Preferably said resin is in the form of a bed of fibres, beads orgranules.

Preferably said beads granules or fibres have a section of from 300 to1600 microns across.

Preferably said resin is a styrene divinyl benzene network copolymerresin.

Preferably said resin has been hypercrosslinked whilst in the swollenstate.

Preferably said resin has in abundance micropores of minimum pore widthof from 5 to 2 Å (mpw).

Preferably the resin has been regenerated after a previous use in asimilar patulin extraction process.

Preferably said regeneration has involved the conversion of the resinheld patulin to a more easily flushed out derivative using ammonia or avolatile base.

Preferably said conversion has involved the at least substantially insitu generation of ammonia or a volatile base from a high pH solution incontact with the resin.

Preferably said regeneration has subsequently involved after flushingout of the patulin derivative(s) the presentation of an acid to theresin.

Preferably the juice is presented to the resin in the range of 20 orgreater bed volumes prior to regeneration of the resin, the bed volumerange being expressed in proportion to a real or notional single juicestrength.

Preferably the juice is presented to the resin at a rate of from about 4to about 10 bed volumes/hour.

Preferably the resin has been tertiary amine functionalised but ispresented to the juice in an acid form as opposed to the free base formthereby reducing the uptake of juice acid during the presentation of thejuice to the resin.

Preferably the resin provides a bed of depth of from 0.5 to 2.0 meters.

In a further aspect the present invention consists in apparatus for usein a process as previously defined, said apparatus having at least onevessel providing a bed of the resin and which is operable in at leasttwo modes, the first mode being that which presents juice to andharvests juice from the resin and the second mode being that whichregenerates the resin.

In still a further aspect the present invention consists in a method ofregenerating a micropored resin which contains patulin in microporeswhich comprise or includes, in a high pH liquid environment containingthe patalin fouled resin, generating a basic vapour (preferably ammonia)sufficient to convert the micropore held patulin to a more easilyflushed out derivative or derivatives and thereafter flushing thederivative(s) from the micropores.

Preferably ammonia is generated.

Preferably the high pH liquid environment is 10 or above.

Preferably the resin after the flushing step is presented to an acid.

In another aspect the present invention consists in, in a patulinreducing process of a fruit juice, the use of a styrene divinyl benzenenetwork co-polymer resin in the form of spherical beads or granules orfibres in sufficient quantities and with a sufficient proportion ofmicropores with a mpw of less than 20 Å.

In some forms said resin has a weak base functionality.

Preferably said beads or granules or fibres (preferably beads orgranules) having a section of between 300-1600 microns across are used.

In a further aspect the present invention consists in a process forreducing the patulin concentration in a fruit juice or fruit juices(hereafter juice) comprising or including the steps of presenting thejuice to a styrene-divinyl benzene network co-polymer resin beads orgranules (preferably spherical) in sufficient numbers for the volume ofjuice being present so that it achieves a desired patulin reduction overthe contact.

In still a further aspect the present invention consists in a processfor reducing the patulin content of a fruit juice which comprises

(i) presenting the fruit juice in suitable apparatus to beads orgranules or fibres of a styrene-divinyl benzene network co-polymer resinthat has been hyper cross linked in the swollen state and has a surfacesubstantially devoid of mesopores and macropores yet has micro pores inabundance, and

(ii) harvesting from such apparatus the fruit juice with a reducedpatulin content.

Preferably the resin has been functionalised to facilitate wetting priorto its contact with the fruit juice.

Preferably said functionalising has been weak base functionalised.

Preferably said apparatus is apparatus of any of the kinds hereinafterdescribed.

Preferably the resin is regenerated using ammonia or a volatile base.

Preferably the use of ammonia or volatile base follows resin contactwith strong alkali.

Preferably said strong alkali is sodium or potassium hydroxide.

Preferably the regeneration involves the provision of an acid rinsefollowing exposure of the resin to ammonia gas or the substitutevolatile base.

In a further aspect the present invention consists in apparatus forreducing the patulin concentration in a fruit juice or fruit juiceswhich includes a vessel holding a quantity of styrene-divinyl benzenenetwork co-polymer resin beads or granules in a manner such that athrough-put of juice can be presented to the resin thereof and whichallows between process runs of juice through the vessel the flushing ofthe resin with regenerative liquid(s) and/or gas(es).

In still a further aspect the present invention consists in a processfor reducing patulin concentration in a fruit juice which comprisespresenting the juice to beads or granules of a styrene-divinyl benzenenetwork co-polymer resin having micropores of less than 20 Å mpw.

Preferably said beads, granules or fibres have a section of from300-1600 microns across.

Preferably said beads or granules or fibres are substantially devoid ofmesopores and macropores.

In still a further aspect the present invention consists in a processfor reducing patulin concentration in a fruit juice which comprises orincludes presenting thejuice to beads or granules of a styrene-divinylbenzene network co-polymer resin having pores which are almostexclusively micropores of less than 20 Å mpw (ie; is low orsubstantially devoid of mesopores and macropores).

Preferably said beads, granules or fibres have a section of from 300 to1600 microns.

Preferably said resin has a low mercury intrusion (e.g. <100).

Preferably said resin has been hypercrosslinked whilst in the swollenstate.

Whilst reference is made herein to the process vessel being prepared forthe extraction of patulin nothing herein precludes the option ofadmixing with the resin beads (or granules or fibres) (or layering inconjunction therewith or separate therefrom or using upstream ordownstream thereof) other ion exchange media the function of which maydiffer from, be ancillary to, or otherwise act in a way different fromthat of the preferred resins of the present invention.

As used herein in respect of the pore size the terms micropore, mesoporeand macropore have the following IUPAC meanings:

“micropore”—pores with a m.p.w. in the range of less than 20 Å.

“mesopores”—pores with a m.p.w. in the range of 20 to 500 Å.

“macropores”—pores with a m.p.w. in the range of greater than 500 Å.

As used herein the terminology “BV” or “bv” refers to bed volumes (i.e.the volume equal to the volume of resin contained in the processingvessel).

As used herein the term “juice” includes within its ambit optionallypretreated fruit juices (eg; concentrated, ultrafiltrated, etc.) and/orblended and/or diluted fruit juices.

As used herein the terms beads or granules or fibres whilst described inthe disjunctive do not rule out a mix thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

Preferred forms performing the present invention will now be describedwith reference to the accompanying drawings in which;

FIG. 1 is a flow diagram of a conventional process for manufacturingapple juice save for the fact that it includes preferably after apreferred ultra filtration or other filtration (eg; diatomaceous earth)stage, a system for reducing patulin levels prior to the concentrationof the juice,

FIG. 2 is a diagram of preferred apparatus in accordance with thepresent invention,

FIG. 3 shows in longitudinal cross section a typical underbed strainer(eg; ofthe kind indicated in FIG. 2 as 28), such a strainer forming partof conventional type apparatus (such as discussed in “Commercialisationof Absorber Technology in the Fruit Juice Industry”, Fruit Processing4-96, R Lyndon, the full content of which are hereby here included byway of reference),

FIG. 4 is a juice and regenerant inlet distributor (referred to as 26 inFIG. 2),

FIG. 5 is a photograph (2500× magnification) of the preferred resin(Alimentech P570) of the present invention showing the surface of thebead,

FIG. 6 is a similar photograph to FIG. 5 but showing the surface of thebead magnified by 10,000 times,

FIG. 7 is a similar photograph to that of FIG. 5 but of a typicalstyrene-divinyl benzene adsorbent polymer with a high level of mesoporesand macropores (the photo being shown at 2500 time magnification),

FIG. 8 is a surface of the same bead depicted in FIG. 7 but at 10,000times magnification, again showing the high level of mesopores andmacropores in a typical styrene-divinyl benzene adsorbent polymer (forexample as disclosed in U.S. Pat. No. 4,297,220 of Rohm and Hass Companyand U.S. Pat. No. 4,439,458 of the Coca-Cola Company hereby bothintroduced by way of reference),

FIG. 9 is a complex plot in respect of trials using a partial applejuice concentrate (25° Brix) (SAMPLE A) and a preferred syntheticadsorbent resin media of the present invention (Alimentech P570) todemonstrate the regenerative nature of the media (for example, byplotting results for process cycles 23, 26 and 27—each cycle being onepresentation of the media to the juice for the purpose of patulinremoval and thereafter one regeneration), the plot showing (i)concentration of patulin (μg/l) against the volume of apple juiceprocessed (BV), (ii) the absorbance at 325 nm of Total Polyphenolicsagainst volume of apple juice processed (BV), and (iii) the relationshipof ° Brix against bed volume,

FIG. 10 is a similar plot to that of FIG. 9 but in respect of a similarpartial concentrate (25° Brix) (SAMPLE A) using a different media(Alimentech P700) showing as against the media (Alimentech P570) of FIG.9 (by plotting cycles 9, 12 and 13) the greater reduction in colourarising from the greater absorbance at 325 n.m of Total Polyphenolics ofthe juice,

FIG. 11 shows for a different source of apple juice partial concentrate(25° Brix) (SAMPLE B) (again using the media of FIG. 9, ie; AlimentechP570) and for process cycle 28 the relationship of (i) pH to volume ofapple juice processed, (ii) the conductivity with respect to volume toapple juice processed, (iii) titratable acid against volume of applejuice processed, (iv) absorbance of total polyphenolics and absorbentsagainst volume of apple juice processed, and (v) ° Brix and patulinconcentration against volume of apple juice processed,

FIG. 12 is a similar plot to that of FIG. 11 (SAMPLE B also) but whereAlimentech P700 has been used and in respect of an earlier process cycle(process cycle 14), and

FIG. 13 is a flow diagram of the preferred resin regeneration process.

The present invention in its preferred form can commercially reducepatulin in fruit juice and concentrates made from fruit juice usingequipment and engineering techniques used in existing applications ofadsorbent polymers and ionic exchange resins in the food industry. Seefor example the machinery referred to by R Lyndon in the previouslymentioned reference.

The present invention in its preferred forms provides an economicallyviable method for reducing patulin by typically in the order of 90% fromclarified apple juice with a synthetic adsorbent resin having clearlydefined characteristics. Contained in a suitably designed and engineeredsystem, the synthetic adsorbent resin can be repeatedly cycled betweenadsorbing patulin and rejuvenated by a unique regeneration process.

Whilst the primary application is patulin reduction in apple juice thereis no reason to expect that patulin will not be reduced from other fruitjuices (e.g. peaches, pears, bananas, pineapples, apricots, cherries andgrapes) with the described process.

Also of importance, the preferred synthetic adsorbent resins willpreferably not remove colour from the apple juice to be processed. Thisis an important consideration, as colour reduction is often not requiredby juice processors. However if colour reduction of juice is required itcan or may be achieved by inclusion of a suitable adsorbent into theprocessing vessels in addition to the patulin reducing resin.

The apparatus depicted hereinafter in FIGS. 2, 3 and 4 are described asfollows:

(A) FIG. 2

1. Clear Fruit juice inlet.

2. Alkali inlet (concentrated sodium or potassium hydroxide) fordilution to 1% w/v and 2% w/v with dilution water.

3. Ammonia inlet (commercial ammonia solution diluted to 0.5% w/v withdilution water).

4. Dilute Citric acid inlet or Phosphoric Acid inlet.

5. Raw water inlet (Potable factory water).

6. Soft water inlet (water free from hardness salts so that hardnessprecipitation does not occur when diluting caustic soda).

7. Raw water isolation valve.

8. Soft water isolation valve.

9. Fruit juice feed pump.

10. Alkali injection Pump.

11. Ammonia injection pump.

12. Acid injection pump.

13. Water pump.

14. Fruit juice flow control valve.

15. Fruit juice flow Meter/Transmitter.

16. Fruit juice inlet isolation valve.

17. Alkali injection/isolation valve.

18. Ammonia injection/isolation valve.

19. Acid injection/isolation valve.

20. Water flow Meter/Transmitter.

21. Regenerant injection isolation valve.

22. Regenerant dilution water isolation valve.

23. Up Flow water control and isolation valve.

24. Sweeten off/Rinse valve.

25. Adsorbent resin containment/Process vessel.

26. Process vessel inlet distributors

27. Bed of adsorbent resin.

28. Under-bed strainers/Distributors. Fruit juice and regenerantcollectors.

29. Up flow outlet valve.

30. Conductivity Meter/Transmitter.

31. Treated juice outlet valve.

32. Regenerant and rinse outlet to drain valve.

33. Regenerant outlet to effluent tank valve.

34. Effluent tank.

35. Treatedjuice outlet.

36. Inlet to effluent tank.

37. Vent to atmosphere.

38. Mixer.

39. Effluent discharge pump.

40. Effluent outlet valve.

41. Outlet to drain/Effluent Discharge.

(B) FIG. 3—an under bed strainer to retain resin within the processvessel (such strainers being arrayed at the bottom of the vessel toprovide containment of the resin and even distribution and collection ofthe treated juice and the regenerants

42. Stainless steep cap.

43. Wedge profile wire, helically wound and welded to longitudinal tiewires.

44. Stainer “gap”—typically 200-300 micron.

45. Bottom cap.

46. Threaded nipple for fitting into common mainfold.

47. Longitudinal tie wire.

(C) FIG. 4 (Detail of inlet juice and regenerant distributors within theprocess vessel) the distributors being arranged to provide evendistribution of juice and regenerant onto the top of the adsorbent resinbed.

48. Inlet pipe.

49. Distributor top disk.

50. Spacer.

51. Distributor bottom disk.

The Adsorbent Polymer.

Screening trials were conducted to determine the most effectiveadsorbents for patulin with apple juice containing approximately 200μg/l of patulin. These were conducted by contacting 150 ml of applejuice with 10 ml of trial adsorbent resin at ambient temperature for 3hours. Throughout the contact period the containment flask was shakenwith a laboratory shaker. At the completion of the contact time thecontacted juice was analysed for patulin using an established method.

We have noted that patulin is adsorbed by resins that have a highpercentages of mesopores and macropores, but the capacity to retainpatulin is limited, presumably, because other hydrophobic chemicalspecies which are not size excluded from the pores are preferentiallyadsorbed and displace patulin. The overall capacity of these resins toeconomically adsorb and retain patulin is therefore limited.

The most effective adsorbents were those with a high surface areacharacterised by a high percentage of micropores.

The most preferred resins tested were those high in micropores andcorrespondingly very low in mesopores and macropores.

The most preferred resins are the P570 and P700 Alimentech resins ofourselves. The latter with its greater mercury intrusion characteristicthan that of Alimentech P570 has more affect on colour of apple juice.Other resins are those of Purolite International Limited referred tobelow.

All such resins are capable of being manufactured using theDavankov—Tsyrupa technology. See in this respect for example U.S. Pat.No. 3,729,457, V. A. Davankov and M. P. Tsyrupa, Reactive Polymers, 13(1990), 27-42, and M. P. Tsyrupa et al, Reactive Polymers, 19 (1993)55-66.

They can perhaps best be characterised by their method of synthesis i.e.that cross-linking occurs whilst the polymer is in a swollen state.

Table 2 collects some relevant static characteristics of some resins ofthis kind available from Purolite International Ltd or ourselves.

TABLE 2 Purolite Purolite Alimentech Purolite Purolite PuroliteCharacteristics MN-100 MN-200 Alimentech P570 P700 MN-400 MN-500 MN-150Surface area,  900-1100  900-1100 1000-1500  900-1100  900-1100 900-1100  900-1200 m²/g (BET) d₅₀, A 850-950 850-950 <100  850-950850-950 850-950 300-400 (Hg intrusion) Pore volume,   1-1.1   1-1.1micropores 0.5   1-1.1   1-1.1   1-1.1 0.6-0.8 ml/g (dry) mesopores <0.1macropores <0.1 Functionality WBA — WBA WBA SBA SAC WBA Volume 0.1-0.2 —0.2-0.4 0.2-0.4 0.2-0.4 0.8-1.0 0.1-0.3 capacity, eq/l Moisture, % 58-61— 42 58-61 58-61 53-56 52-55 Strong base 10-20 — 10—20 10-20 >95 — 10-20capacity, Expansion, % <5 — <5 <5 <5 <5 <5 (ionic forms)

Three porosity classes have been selected for this broad, first seriesof resins: (i) Alimentech P570, (ii) Purolite MN-150, and (iii) thegroup Purolite MN-100, MN-200, MN-400 and MN-500 and Alimentech P700. Itshould be remembered that BET and mercury intrusion porosimetries arecarried out on dried shrunken materials, so the recorded values arereal, and reproducible, but at best proximate.

The chosen functionalities are those historically selected inion-exchange applications:

1. SBA—strong base anion, quaternary ammonium.

2. WBA—weak base anion, tertiary amine.

3. SAC—strong acid cation, sulfonic acid.

Two most preferred adsorbent resins to effectively adsorb and retainpatulin from the apple juice are Alimentech P570 and Alimentech P700available from us.

These are both styrene—divinyl benzene network copolymers withDavankov—Tsyrupa type “hyper crosslinking”.

Alimentech P570 is a very highly cross linked polystyrenic networkproduced by hypercrosslinking in the swollen state (small low porediameters (<100 d₅₀ A)). This resin is characterised by having very fewmesopores and macropores and a very high percentage of micropores(minimum pore width <20 Angstroms).

These preferred adsorbent resins were transferred to laboratory columns,which are scaled down from full size process vessels. Process trialswith the two polymers show that patulin could be removed from applejuice solution at economic cycle lengths of at least 30 bed volumes.

Of particular importance is the fact that Alimentech P570 has virtuallyno mesopores or macropores. See FIGS. 5 and 6 and contrast them withFIGS. 7 and 8. The absence of these larger pores means that colourbodies in the juice are not adsorbed. Therefore the colour of the juiceis not reduced when contacted with the adsorbent resin. Trial resultsshow colour is not reduced by more than 1.5% (AU measured at 420 nm).Colour reduction is sometimes a requirement, but most often colourreduction is specifically not required by a processor.

A further advantage of these synthetic adsorbent polymers is that theyhave a microporous structure. Molecules that would normally displacepatulin are size excluded from being adsorbed.

Standard styrene—DVB, polyester and acrylic resins can show a capacityto adsorb patulin but do not have such a “tight” porosity, and thereforehave limited capacity. See FIGS. 7 and 8. However other resin typesotherwise having the characteristics specified can be used.

Non functionaries synthetic polymers of kind required with an abundanceof micropores can sometimes be difficult to wet—amination with atertiary amine (or any other means of providing a weak basefunctionality) ensures wetability of the micropores allowing passage ofaqueous solution into them.

Alimentech P570 is aminated with tertiary amine to provide the preferredweakly basic capacity. The weak base functionality assists the wettingof the resin.

2. Regeneration:

Conventional adsorbent regeneration with aqueous caustic is not suitablefor desorbing patulin because hydration of the hydroxyl ion sizeexcludes it from the micropores of the adsorbent. Organic solvents arenot practical based on cost and difficulty in handling and the need toensure thorough removal from the resin before the resin bed is returnedto being contacted with fruit juice.

Patulin is desorbed from the resin at elevated pH. It was necessary touse a base that would migrate into the micropores of the resin. Trialswere conducted with the use of ammonium hydroxide as a volatile base.This has proven to be very successful and unique.

We believe our use of ammonia gas, produced in situ by mixing diluteammonia solution with dilute caustic soda or caustic potash just priorto entering the resin containment vessel and allowing the ammonia todiffuse into the micropores of the resin, is a new method ofregeneration. The success of this regeneration procedure is demonstratedin the data presented hereafter. Nevertheless any other patulindegrading volatile base may be used.

Practical Application:

The process of reducing patulin from clarified fruit juice may beengineered to provide a commercial process. Practical plant may beconstructed using conventional engineering techniques used in theapplication of ion exchange and other adsorbent polymers used in thewater and food processing industries.

Equipment may be constructed from stainless steel and designed toprocess at any flow rate encountered in practice. Typical flow rateswill be 2,000 liters per hour to 30,000 liters per hour.

Either fresh, single strength juice or reconstituted juice fromconcentrate may be used.

Alimentech P570 (the preferred media) is contained in a suitably sizedprocessing vessel and retained by a system of strainers located in thebottom of the vessel.

By a series of connected pipework and valves, pipes and tanks, the resincontained within the vessel can be contacted with juice during the resinexhaustion or juice process cycle, and various regenerants during therejuvenation or regeneration cycle.

A single processing vessel provides batch operation with the vesselalternating between juice processing for patulin reduction andregeneration or rejuvenation.

Continuous processing is achieved by using equally sized vessels. Onevessel is processing whilst the other is being regenerated. The vesselsare sized to contain enough resin so that the processing time for thejuice exceeds the regeneration time.

A continuously processing machine may be installed in as part of thejuice production facility so that all, part or none of the juice may bepassed through the adsorbent resin bed.

Processing Procedure: (Refer to FIGS. 1 to 4 and 13).

The process is completed in a number of steps carried out in apredetermined order. The following steps are required to complete a fillcycle from the commencement of the cycle to the time the cycle is readyto begin again.

Step

Description

1. Sweeten-on:

Water from the previous cycle (final step of the regeneration) isdisplaced by juice, which is pumped into the vessel from the juice feedsupply. The displaced water is diverted to drain or may be recycled to awater reuse system. Juice flow rate 5-10 bed volumes per hour.

Completion of the sweeten-on step may be determined by either the volumeof the influent juice or sensing the presence of juice at the outlet ofthe vessel with a suitable instrument. (conductivity, refractive index,mass flow etc).

Flow description:

Juice into clear juice inlet (1). Juice flow controlled at flow controlvalve (14). Juice flows into process vessel through valve (16). Juicedistributed onto adsorbent resin bed through juice inlet distributors(26). Water displaced from resin bed is collected in the under bedstrainer/distributor system (28) and diverted to the drain (41) viaRegenerant and rinse outlet to drain valve (32).

Condition to advance:

Volume, conductivity, Brix.

2. Juice Process:

Also known as exhaustion cycle. Juice is processed down flow through theresin bed at a flow rate in the range 5-10 bed volumes per hour. Duringthis cycle patulin is adsorbed into the pores of the resin. The juiceprocess step continues until the capacity of the resin to adsorb patulinis exceeded. This point is established by analysis of the juice forresidual patulin, and retrospectively applied to subsequent processingcycles. Once the predetermined juice volume as measured with a suitablevolume measuring device the next step begins

Flow description:

Juice into clear juice inlet (1). Juice flow controlled at flow controlvalve (14). Juice flows into process vessel through valve (16). Juicedistributed onto adsorbent resin bed through juice inlet distributors(26). Having passed through the adsorbent bed the treated juice iscollected by the under bed strainer/distributor system (28) and divertedvia Treated juice outlet valve (31) to the treated juice outlet (35).

Condition to advance:

Volume (measured with flow meter (15)).

3. Sweeten Off:

At the completion of the exhaustion step the juice is displaced withwater at 5-10 b.v. per hour to ensure that the maximum amount of juiceis recovered to the product collection tank. The completion of sweetenoff is determined by either the volume of the influent water or sensingthe reduced juice concentration at the outlet of the vessel with asuitable instrument (conductivity, refractive index, mass flow etc).

Flow description:

Raw potable water enters via valve (5) and isolation valve (7), ispumped (13) into the top of the resin containment/processing vessel viasweeten off valve (24). Juice contained in the vessel is displaceddown-flow through the bed collected in the under bedstrainer/distributor system (28) and diverted via valve (31) to thetreated juice outlet (35).

4. Backwash:

Water is passed up-flow through the resin bed at a flow rate of about 6meters/hour . The resin bed is expanded and fluidised to remove anyinsoluble solids filtered on to the bed or channelling within the bedwhich may have occurred on the previous process cycle

Flow description:

Soft water enters via valve (6) and isolation valve (8), is pumped (13)into the bottom of the resin containment/processing vessel at a presetflow rate via the upflow water control valve (23). The backwash water isdistributed up-flow into the resin containment vessel. Water exits thevessel to drain via backwash out let valve (29).

Condition to advance:

Time—10-20 minutes.

5. Settle:

Flow through the bed is stopped, allowing the resin to classify andsettle.

Flow description:

All inlets and outlets to the resin containment/process vessel areclosed so that there is no flow in or out of the vessel.

Condition to advance:

Time—approximately 5 minutes.

6. Alkali Inject:

Resin bed is contacted, down-flow (or up-flow) with alkali solution.Acceptable performance is obtained using 2 b.v. of 2% w/v solution ofeither sodium or potassium hydroxide solution, passed down flow throughthe bed at a flow rate of about 4 b.v. per hour.

Caustic solution raises the pH of the resin to above pH 10 andregenerates the ion exchange sites and converts the tertiary aminegroups into the free base form.

Flow description:

Soft water from inlet (6) and isolation valve (8) is pumped (13) viaflow control valve (22), and regenerant isolation valve (21) into theresin containment/processing vessel (25), distributed onto the resin bedvia the regenerant chemical inlet distributors (26). Concentrated sodiumor potassium hydroxide from inlet (2) is pumped (10) via injection valve(17) and “on-line” diluted to 2% w/v. Having passed down-flow throughthe resin containment/process vessel, the spent solution is collected bythe under bed strainer/distributor system (28) and diverted viaregenerant rinse outlet valve (33) to the effluent discharge (41).

Condition to advance:

Time—30 minutes.

7. Caustic+Ammonia Injection:

Resin bed is contacted, down flow or up flow with solution of causticand ammonium hydroxide. 1 b.v. of solution containing 1% w/v sodium orpotassium hydroxide and 0.5% w/v ammonium hydroxide is passed throughthe bed at a suitable flow rate of about 4 b.v. per hour.

Flow description:

Soft water from inlet (6) and isolation valve (8) is pumped (13) viaflow control valve (22), and regenerant isolation valve (21 ) into theresin containment/processing vessel (25), distributed onto the resin bedvia the regenerant chemical inlet distributors (26). Concentrated sodiumor potassium hydroxide from inlet (2) is pumped (10) via injection valve(17) and “on-line” diluted to 1% w/v. Ammonium hydroxide solution frominlet (3) is pumped (11) via injection valve (18) and “on-line ” dilutedto 0.5% w/v. Having passed down-flow through the process vessel, thespent solution is collected by the under bed strainer/distributor system(28) and diverted via effluent outlet valve (33) to the effluent tank(34).

Condition to advance:

Time—15 minutes.

8. Caustic+Ammonia Diffusion:

At the completion of the aqueous caustic ammonia solution injection stepflow through the vessel is stopped to allow a holding time ofapproximately 30 minutes enabling diffusion of gaseous ammonia into thematrix of the resin and for patulin to diffuse out from the resinmatrix.

Flow description:

All inlets and outlets to the process vessel are closed so that there isno flow in or out of the vessel.

Condition to advance:

Time—30 minutes.

9. Caustic+Ammonia Displacement:

1 b.v. of displacement water is passed down flow through the bed atsuitable flow rate of about 4 b.v. per hour to displace the causticammonia. The displaced solution is diverted in the effluent tank. (Refer“effluent processing”)

Flow description:

Soft water from inlet (6) and isolation valve (8) is pumped (13) viaflow control valve (22), and regenerant isolation valve (21) into theresin containment/processing vessel (25), distributed onto the resin bedvia the regenerant chemical inlet distributors (26). Having passeddown-flow through the process vessel, the spent solution is collected bythe under bed strainer/distributor system (28) and diverted via effluentoutlet valve (33) to the effluent tank (34).

Condition to advance:

Time—15 minutes.

10. First Fast rinse:

The bed is rinsed from the top of the vessel with 1 b.v. of water atabout 12 b.v. per hour to rinse the majority of the free aqueous causticammonia solution from the resin. The rinse effluent from this step isdiverted to the effluent tank.

Flow description:

Raw water from inlet (6) and isolation valve (8) pumped (13) via rinseinlet valve (24), into the resin containment/processing vessel (25),Having passed down-flow through the process vessel, the rinse solutionis collected by the under bed strainer/distributor system (28) anddiverted via effluent outlet valve (33) to the effluent tank (34).

Condition to advance:

Time—5 minutes.

11. Acid Wash:

Necessary to convert the functional groups on the resin from the freebase form into the acid form to avoid the removal of fruit acid from thesubsequent juice process cycle. Either citric or phosphoric acid may beused to effect the conversion. The effluent from this step is divertedto the effluent tank.

Additional acid is used to ensure that the ammonia in the effluent tankis neutralised and acidified to ensure that free ammonia is notliberated form the effluent solution when it is diverted to the effluentdrain. Typically 2 b.v. of citric acid as a 2% w/v solution is adequateto ensure effluent neutralisation. The flow rate that the acid solutionis applied at may be at typical fat rinse rate of up to 12 bed volumesper hour.

Flow description:

Acid from inlet (4) is pumped (12) via acid injection valve (19), andregenerant isolation valve (21) into the processing vessel (25),distributed onto the resin bed via the regenerant chemical inletdistributors (26). Having passed down-flow through the process vessel,the partially depleted solution is collected by the under bedstrainer/distributor system (28) and diverted via effluent outlet valve(33) to the effluent tank (34).

Condition to advance:

Time—15 minutes.

12. Displacement:

Acid solution is displaced with 1 b.v. of raw potable water at a flowrate of 4 b.v. per hour. The effluent from this step is diverted to theeffluent tank.

Flow description:

Water from inlet (5) and isolation valve (7) is pumped (13) via flowcontrol valve (22), and regenerant isolation valve (21) into theprocessing vessel (25), distributed onto the resin bed via theregenerant chemical inlet distributors (26). Having passed down-flowthrough the resin containment/process vessel, the displaced acidsolution is collected by the under bed strainer/distributor system (28)and diverted via effluent outlet valve (33) to the effluent tank (34).

Condition to advance:

Time—15 minutes.

13. Final Rinse:

Resin bed is rinsed with raw potable water at a suitable rate(approximately 12 b.v. per hour) to remove residues of acid. Completionof final rinse is sensed by the monitoring the conductance of the rinsewater exiting the resin bed. Final rinse water is diverted to drain.

At the completion of the final rinse the resin bed may be returned toservice for the next juice processing cycle to begin.

Flow Description:

Raw water from inlet (6) and isolation valve (8) is pumped (13) viarinse inlet valve (24), into the processing vessel (25), Having passeddown-flow through the resin containment/process vessel, the rinsesolution is collected by the under bed strainer/distributor system (28)and diverted via the rinse outlet valve (32) to the drain (41).

Condition to advance:

Reduced conductivity of rinse outlet indicates that the acid has beenrinsed from the bed.

At the completion of the final rinse the resin bed may be returned toservice for the next juice processing cycle to begin.

Concentration of juice to be processed can be in the range from ≈12°Brix (single strength) to 30° Brix. It is expected the increasedviscosity and osmotic effects would limit the performance atconcentrations above 30° Brix.

The temperature at which the process is conducted will effect theperformance, however all development trials have been conducted atambient temperature with commercially acceptable results. Increasing thetemperature will improve the kinetics of the process (possibly withoutleakage of patulin) but the capacity of the resin will not be increased.

Effluent processing: Effluent from this process does contain ammonia.

Consideration has been given to minimising the egress of ammonia gas bycollecting (bulking) the effluent which contains ammonia into a suitabletank.

The effluent from the acid wash step is added to the ammonia containingeffluent at a rate to ensure that the pH is less than 7 thus preventingthe evolution of ammonia gas. During the time the effluent is divertedto the effluent tank the tank is mixed with a suitable mixer. At thecompletion of the regeneration the contents of the tank is discharged tothe common drain.

Trials with Alimentech P570 and P700 Resins:

A series of screening trials were used to identify the AdsorbentPolymers/Resins which displayed the highest capacities for patulinreduction from apple juice reconstituted from concentrate. It wasimmediately obvious that standard hydrophobic adsorbent polymers, (P420(Alimentech), SP70 (Mitsubishi), XAD16 (Rohm & Haas), SP207(Mitsubishi), etc.), used for decolourisation of juice displayed limitedcapacity for patulin, interpreted to be due to competition for theavailable adsorption sites by other larger components in the juice whichare capable of multi-site hydrophobic interactions. The highest capacitywas displayed by Alimentech P570 and Alimentech P700. Both AdsorbentResins are lightly functionalised with tertiary amine groups and therebycomply with FDA regulations. Both also have a preponderance ofmicropores eliminating the competition from the larger hydrophobiccompounds in a juice which are size excluded from the large portion ofthe available adsorption surface. Evaluation of both of these adsorbentresins were progressed to laboratory scale column trials.

Juices of the Trials:

SAMPLE A.

Apple juice reconstituted to 25° Brix from concentrate. The partialconcentrate was moderately coloured with a higher than typical totalpolyphenol content. During this series of trials the detected level ofpatulin in the juice decreased from 98 μg/l to 13 μg/l corrected to 12°Brix.

SAMPLE B.

25° Brix apple juice reconstituted from concentrate. This partialconcentrate was lower in colour and total polyphenolics than the SAMPLEA juice. During these trials patulin was reduced from 78 μg/l to 12 μg/lcorrected to 12° Brix.

Adsorbent Resins:

A. Alimentech P570, 100 ml in a ½″ column giving ˜600 mm bed depth. Theresin sample had been cycled with apple juice twenty two timespreviously. The resin was stored layed-up in 2% caustic solution andhence was conditioned by cycling once with phosphoric acid beforeinitiating a standard patulin regeneration followed by five monitored,sequential processing cycles using SAMPLE A high patulin juice, andfinally by one cycle with SAMPLE B juice.

B. Alimentech P700, 100 ml in a ½″ column, providing an ˜600 mm b.v.depth. The adsorbent resin was preconditioned from new with eight cyclesusing apple partial concentrate prior to conducting five monitored,sequential processing cycles treating SAMPLE A high patulin juice,followed by one cycle using SAMPLE B juice.

Procedure:

The selected concentrate was reconstituted to 25° Brix and thirty bedvolumes pumped through the bed at 6 b.v./hr, at ambient temperature. Theperformance of the resins are predicted to be diffusion rate dependentso flow rates are important. Five samples were drawn through each of theservice cycles and analysed to determine the patulin and polyphenolleakage profiles. The results are displayed in FIGS. 9 to 12.

Tables 3 to 5 exhibit the typical feed juice analysis, plus theconcentrations of indicative components in selected treated compositesamples, after normalisation to 25° Brix. The results were selected todemonstrate performance trends, the other results are available uponrequest.

TABLE 3 Results: Analyses of the Patulin Reduced Composites of SAMPLE Aapple juice partial concentrate treated through Alimentech P570. ReferFIG. 9: Typical untreated Process Process Process Analyses feed cycle 23cycle 26 cycle 27 Volume treated bv 30.0 30.3 30.5 30.6 pH 3.6 3.7 3.73.7 Soluble solids ° Brix 25.0 24.1 24.0 24.22 Conductivity at 20° C.μS/cm 3190 3220 3190 3130 Abs₃₂₅ of total polyphenolics¹ AU 0.945 0.822(−13%) 0.825 (−13%) 0.829 (−12%) Absorbance¹ 420 nm 1.200 1.195 (<−1%)1.192 (<−1%) 1.186  (−1%) 1 cm cell path 560 nm 0.154 0.154 (0%) 0.153(<−1%) 0.157  (+2%) Patulin¹ μg/l 210 14 (−93%) 28 (−87%) 27 (−87%)Patulin converted to 12° Brix² μg/l 98 6 13 13 ¹The total polyphenolics,absorbance and patulin results have been normalised to 25° Brix for easeof comparison. ²The World Health Organisation guideline limit forpatulin is 50 ppb, ˜50 μg/l at 12° Brix.

TABLE 4 Analyses of the Patulin Reduced Composites of Sample A applejuice partial concentrate treated through Alimentech P700 Refer FIG. 10:Typical Process Process Analyses untreated feed Process cycle 9 cycle 12cycle 13 Volume treated bv 30.0 30.6 30.8 30.6 pH 3.6 3.6 3.6 3.6Soluble solids ° Brix 25.0 23.9 24.0 23.8 Conductivity at 20° C. μS/cm3150 3110 3150 3120 Abs₃₂₅ of total polyphenolics¹ AU 0.930 0.183 (−80%)0.246 (−74%) 0.246 (−74%) Absorbance¹ 420 nm 1.166 0.609 (−48%) 0.655(−44%) 0.650 (−44%) 1 cm cell path 560 nm 0.146 0.071 (−51%) 0.078(−47%) 0.081 (−45%) Patulin¹ μg/l 250 16 (−94%) 22 (−91%) 21 (−92%)Patulin converted to 12° Brix² μg/l 114 7 10 10 ¹The totalpolyphenolics, absorbance and patulin results have been normalised to25° Brix for ease of comparison. ²The World Health Organisationguideline limit for patulin is 50 ppb, ˜50 μg/l at 12° Brix.

TABLE 5 Results continued: Comparison of the analyses of the PatulinReduced Composites for the Alimentech P570, or P700, treated SAMPLE Bapple juice partial concentrate. Refer FIG. 11 Refer FIG. 12 Typicaluntreated P570 Pro- P700 Pro- Analyses Juice cess cycle 28 cess cycle 14Volume bv 30.0 30.2 30.6 pH 3.5 3.6 3.5 Soluble solids ° Brix 25.0 24.023.8 Conductivity at 20° C. μS/cm 2900 2880 2900 Abs₃₂₅ of totalpolyphenolics¹ AU 0.630 0.599  (−5%) 0.206 (−67%) Absorbance¹ 420 nm0.669 0.655  (−2%) 0.385 (−42%) 1 cm cell 560 nm 0.077 0.067 (−13%)0.046 (−40%) Patulin¹ μg/l 170 26 (−85%) 13 (−92%) Patulin converted to12° Brix² μg/l 78 12 6 ¹The total polyphenolics, absorbance and patulinresults have been normalised to 25° Brix for ease of comparison. ²TheWorld Health Organisation guideline limit for patulin is 50 ppb, ˜50μg/l at 12° Brix.

FIG. 9 compares the patulin and total polyphenolic leakage profiles forselected process cycles through Alimentech P570, and FIG. 10 displaysthe analogous data for the process runs through Alimentech P700. In FIG.9 the concentration of Patulin (μg/l) is plotted against Volume of 25°Brix Apple Juice Processed whilst Soluble Solids (° Brix) is alsoplotted against the same Volume axis. In the plot:

42 is Bed Volume vs Concentration of Patulin (μg/l) for Process Cycle23,

43 is Bed Volume vs Concentration of Patulin (μg/l) for Process Cycle26,

44 is Bed Volume vs Concentration of Patulin (μg/l) for Process Cycle27,

45 is Bed Volume vs Absorbance of Total Polyphenolics (AU) for ProcessCycle 23,

46 is Bed Volume vs Absorbance of Total Polyphenolics (AU) for ProcessCycle 26,

47 is Bed Volume vs Absorbance of Total Polyphenolics (AU) for ProcessCycle 27, and

48 is Bed Volume vs Soluble Solids (° Brix).

In FIG. 10 Concentration (μg/l) is plotted against V volume of 25° BrixApple Juice processed. Also plotted are Soluble Solids (° Brix) againstthe same Volume axis. Also shown against the Volume axis is theAbsorbance of Total Polyphenolics (AU).

In the plot of FIG. 10:

49 is Bed Volume vs Concentration of Patulin (μg/) for Process Cycle 9,

50 is Bed Volume vs Concentration of Patulin (μg/l) for Process Cycle12,

51 is Bed Volume vs Concentration of Patulin (μg/l) for Process Cycle13,

52 is Bed Volume vs Absorbance of Total Polyphenolics (AU) for ProcessCycle 9,

53 is Bed Volume vs Absorbance of Total Polyphenolics (AU) for ProcessCycle 12,

54 is Bed Volume vs Absorbance of Total Polyphenolics (AU) for ProcessCycle 13, and

55 is Bed Volume vs Soluble Solids (° Brix).

FIGS. 11 and 12 focus upon the different leakage profiles for the juicecharacteristics monitored resulting from treatment by P570, and P700respectively.

In FIG. 11 there is shown a plot of Soluble Solids (° Brix) and Patulin(μg/l) against Volume of 25° Brix Apple Juice Processed. Also plottedagainst the same Volume axis is pH. In addition, also against the sameVolume axis is Conductivity (μS/cm). Still also plotted is theAbsorbance of Total Polyphenolics (AU) and Absorbance and this is againagainst the same Volume axis. In the plot of FIG. 11:

56 is Bed Volume vs pH,

57 is Bed Volume vs ° Brix,

58 is Bed Volume vs Patulin (μg/l),

59 is Bed Volume vs Conductivity (μS/cm),

60 is Bed Volume vs Abs of Total Polyphenolics (AU),

61 is Bed Volume vs ‘Colour’ Absorbance at 420 nm,

62 is Bed Volume vs ‘Colour’ Absorbance at 560 nm.

FIG. 12 plots Soluble Solids (° Brix) and Patulin (μg/l) against Volumeof 25° Brix Apple Juice Processed. As with FIG. 11 pH is also plottedagainst the same Volume axis. Also plotted is Conductivity (μS/cm)against the same Volume axis. Finally also plotted is Absorbance ofTotal Polyphenolics (AU) and Absorbance against the same Volume axis. Inthe plot:

63 is Bed Volume vs pH,

64 is Bed Volume vs ° Brix,

65 is Bed Volume vs Patulin (μg/l),

66 is Bed Volume vs Conductivity (μS/cm),

67 is Bed Volume vs Absorbance of Total Polyphenolics (AU),

68 is Bed Volume vs ‘Colour’ Absorbance at 420 nm, and

69 is Bed Volume vs ‘Colour’ Absorbance at 560 nm.

All of the plots of FIG. 12 are in respect of process cycle 14.

Note the use of Alimentech P700 has the effect of much greater colourreduction (ie; −42% at 420 nm as opposed to only −2% with AlimentechP570 for SAMPLE B).

Patulin Analysis:

The patulin analyses were conducted using Reversed-phase HighPerformance Liquid Chromatography using standard methods.

What we claim is:
 1. A process for reducing the patulin content in afruit juice which comprises or includes (i) presenting the juice to aresin material having in abundance micropores of less than 20 Å minimumpore width and at least a pore surface capable of retaining patulin bythe forces of chemisorption, and (ii) harvesting the juice with areduced patulin content from step (i).
 2. A process of claim 1 whereinthe resin has weak base functionality.
 3. A process of claim 1 whereinsaid resin is substantially devoid of mesopores and macropores.
 4. Aprocess of claim 1 wherein the abundance of micropores is of a sizecapable of receiving patulin yet having a minimum pore widthinsufficiently large to allow alkaline solution conversion of poreretained patulin to a more easily flushed out form.
 5. A process ofclaim 1 wherein said resin has micropores in abundance of less than 15 Åminimum pore width.
 6. A process of claim 1 wherein said resin has inabundance pores of from 5 to 20 Å minimum pore width.
 7. A process ofclaim 1 wherein said resin has very high internal surface areas yet alow mercury intrusion characteristic.
 8. A process of claim 7 whereinsaid resin has a surface area of greater than 900 m²/g (BET).
 9. Aprocess of claim 8 wherein said surface area is from 1000 to 1500m²/g(BET).
 10. A process of claim 7 wherein said resin has a mercuryintrusion (d₅₀,A) of less than
 100. 11. A process of claim 1 whereinsaid resin is in the form of bed of beads, granules or fibers.
 12. Aprocess of claim 11 wherein said beads, granules or fibres have aparticle or transverse section of from 300 to 1600 microns across.
 13. Aprocess of claim 1 wherein said resin is a styrene divinyl benzenenetwork copolymer resin.
 14. A process of claim 13 wherein said resinhas been hypercrosslinked whilst in the swollen state.
 15. A process ofclaim 1 wherein the resin has been regenerated after a previous use in asimilar patulin extraction process.
 16. A process of claim 15 whereinsaid regeneration has involved the conversion of the resin held patulinto a more easily flushed out derivative using ammonia or a volatilebase.
 17. A process of claim 16 wherein said conversion has involved theat least substantially in situ generation or expression of ammonia or avolatile base from a high pH solution in contact with the resin.
 18. Aprocess of claim 17 wherein ammonia gas was expressed.
 19. A process ofclaim 16 wherein said regeneration has subsequently involved, afterflushing out of the patulin derivative(s), the presentation of an acidto the resin.
 20. A process of claim 1 wherein the juice is presented tothe resin in the range of 20 or greater bed volumes prior toregeneration of the resin, the bed volume range being expressed inproportion to a real or notional single juice strength.
 21. A process ofclaim 1 wherein the juice is presented to the resin at a rate of fromabout 4 to about 10 bed volumes/hour.
 22. A process of claim 1 whereinthe resin has been tertiary amine functionalized but is presented to thejuice in an acid form (as opposed to the free base form) therebyreducing the uptake of juice acid during the presentation of the juiceto the resin.
 23. A process of claim 1 wherein the resin provides a bedof depth of from 0.5 to 2.0 meters.
 24. A method of regenerating amicropored resin which contains patulin in micropores which comprises orincludes, in a high pH liquid environment containing the patulin fouledresin, generating ammonia gas or a volatile base sufficient to convertthe micropore held patulin to a more easily flushed out derivative orderivatives and flushing the derivative(s) from the micropores.
 25. Amethod of claim 24 wherein the high pH liquid environment is 10 orabove.
 26. A method of claim 24 wherein ammonia gas is generated.
 27. Amethod of claim 24 wherein the resin after the flushing step ispresented to an acid.
 28. A method of claim 24 wherein the high pHliquid environment is provided by potassium hydroxide, sodium hydroxideor both.
 29. A method of claim 24 wherein said acid is phosphoric acid,citric acid or both.